Visible-Light-Promoted Cross-Coupling Reactions of Aryldiazonium Salts with S-Methyl-d₃ Sulfonothioate or Se-Methyl-d₃ Selenium Sulfonate: Synthesis of Trideuteromethylated Sulfides, Sulfoxides, and Selenides

Abstract

A novel visible-light-photocatalytic deuterated thiomethylation/methylselenation of aryldiazonium salts utilizing S/ Se-methyl-d 3 sulfonothioate has been developed. The mild conditions and the various functional groups provide a green protocol for the efficient and rapid introduction of the S-CD 3 or Se-CD 3 group with useful levels of deuterium content (>91% D). Trideuteromethyl sulfoxides have also been successfully chemoselectively observed by simple atmospheric changes under photocatalytic conditions.

Robust, scalable construction of an electrophilic deuterated methylthiolating reagent: facile access to SCD3-containing scaffolds

“…1b). 20 In view of the importance of S -methyl- d 3 analogues and its limited synthetic routes, a direct and concise transformation for the scalable access of the deuterated methylthiolating reagent remains highly desired and sought after (Fig. 1c).…”

Desulfonylation via Radical Process: Recent Developments in Organic Synthesis

“…Similarly, Wang and co-workers applied their approach to the visible-light-initiated cross-coupling reactions of aryldiazonium salts 155-1 with S-methyl-d 3 sulfonothioates or Se-methyl-d 3 selenium sulfonates 155-11 (Scheme 155B). 554 In this variant, aryl radicals were generated and engaged in radical deuterated thiomethylation/methylselenation. Trideuteromethyl sulfoxides 155-13 had also been successfully observed with 97% D incorporation under atmospheric conditions.…”

Research progress of electrophilic sulfenylation ofbenzenethiosulfonates

“…C-S键, 通过芳基重氮盐与三氘代苯磺酸硫甲酯的自 由基硫化反应制备三氘甲基硫化物, 反应在空气条件 下进行还能实现三氘代亚砜化合物的制备 [65] , 反应还 可以通过4-烷基-1,4-二氢吡啶和苯磺酸硫酯的自由基 交叉偶联来实现硫、亚砜类化合物的高效制备 [66] [91,92] (图26). 芳 基重氮盐在可见光作用下可以与激发态光敏剂发生单 电子转移产生芳基自由基, 从而实现芳环的硫二氟甲 基化、硫三氟甲基化 [93,94] (图27(a, b)), 芳环的硫三氟 甲基也可以通过芳基胺为原料通过中间体芳基重氮盐 产生 [95] (图27(c)).…”